Carotenoid
DATA No : VCA0017
INFORMANT : Masayoshi Ito
NAME : (3R,3'R)-3,3'-Dihydroxy-
b,
b-carotene-4,4'-dione
| COMMON NAME | : | (3R,3'R)-Astaxanthin |
| SYMBOL | : | |
| FORMULA | : | C40H52O4 MOL.WT (average) : 596.838 |
| PHYSICAL AND CHEMICAL PROPERTIES |
| MELTING POINT | : | |
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| BOILING POINT | : | |
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| REFRACTIVE INDEX | : | |
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| OPTICAL ROTATION | : | |
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| DENSITY | : | |
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| SOLUBILITY | : | |
| UV SPECTRA | : | lmax (nm) (e): CHCl 3492 (1920) (Ref. 0010/0077) |
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| IR SPECTRA | : | nmax(KBr)/cm-1: 3486m (OH), 1664s (conj. CO), 1607m, 1557s (C=C), 1399w, 1390m, 1366w (gem. Dimetyl), 1076s, 1039m (OH) and 969s (CH=CH, trans)
[Spectrum 0003] (Ref. 0010/0077) |
|
| NMR SPECTRA | : | 1H-NMR d(500 MHz, CDCl3): 1.21 and 1.32 (each 6H, s, 1, 1'-gem-Me), 1.81 (2H, t, J 13, 2, 2'-Hax), 1.94 (6H, s, 5, 5'-Me), 1.98 and 2.00 (each 6H, s, 9, 9', 13, 13'-Me), 2.16 (2H, dd, J 6 and 13, 2, 2'-Heq), 3.67 (2H, d, J 2, 3, 3'-OH), 4.32 (2H, ddd, J 2, 6 and13, 3, 3'-H) and 6.20-6.70 (14H, m, olefinic-H) (Ref. 0068/0077)
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| MASS SPECTRA | : | m/z: 596 (M), (M-16), (M-16-16), (M-79), (M-92), (M-106), (M-92-16), (M-106-16), (M-154), (M-167), (M-207), (M-219), (M-233) (Ref. 0058/0077)
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| OTHER SPECTRA | : | CD data in EPA solution (25 C): De 240 (+20.0), 252 (0), 270 (-20.0), 284 (0), 314 (+34.0), 355 (0), 372 (-3.0) (Ref. 0421)
|
TLC (Kieselgel 60 Merck, CH2Cl2-acetone-formic acid 95:5:3) Rf = 0.3 --- (3S,3'S)-astaxanthin (
Ref. 0010)
HPLC (column: Sumipax OA-2000 (10
mm) 0.4
25 cm, eluent: hexane-CH2Cl2-EtOH 48:16:0.6, flow: 0.8 ml/min) tR = ca. 57 min (3R,3'R), ca. 60 min (meso), ca. 64 min (3S,3'S)
[
Chromatogram 0004] (
Ref. 0069/
0070/
0210)
HPLC (column: LiChrosorb SI 60 (5
mm) 0.32
50 cm, eluent: hexane-ethyl acetate-acetonitrile 88:10:2, flow: 0.8 ml/min) tR = ca. 42 min (diacetate of all-E isomer)
[
Chromatogram 0005] --- racemic astaxanthin (
Ref. 0071)
HPLC (columun: TSK gel ODS-80Ts (Tosoh) 0.46
15 cm, eluent and flow: 1.0 ml/min, H2O-MeOH 5:95 for 5 min, follwed by 5 min-linear gradient MeOH-THF 7:3, and then MeOH-THF 7:3 for 5 min)
b-carotene, echinenone,
b-cryptoxanthin, 3-hydroxy-echinenone, cantaxanthin, 3'-hydroxy-echinenone, cis-adonixanthin, adonirubin, adonixanthin and astaxanthin were separated. tR = 6.30 min for astaxanthin (
Ref. 0208).
Separation of (3S,3'S), (3S,3'R) and (3R,3'R) astaxanthin by HPLC on a Pirkle covalent L-leucine column (
Ref. 1164).
Phaffia rhodozyma (Xanthophyllomyces dendrorhous) (yeast) (
Ref. 0425)
Homarus gammarus (Lobster) (
Ref. 0418)
Salmo salar, Oncorhynchus (salmon) (
Ref. 0419)
Asterias rubens (starfish) (
Ref. 0420)
Shrimps and lobsters (
Ref. 0421)
Euphausia superba (antarctic krill) (
Ref. 0422)
Asterina pectinifera, Asterias amurensis (starfish) (
Ref. 0423)
Watasenia scintilans, Sepia modokai, Sepia officinales (cuttlefish) (
Ref. 0424)
Octopus vulgaris, Octopus ocellatus, Octopus minor (octopus) (
Ref. 0424)
The Wittig condensation of C10-dialdehyde with 2 equiv. of C15-phosphonium salt and subsequent thermal isomerization afforded astaxanthin.
(3S,3'S)- and (3R,3'R)-Astaxanthin --- Enantiomeric chiral blocks of C15-phosphonium salts were synthesized via three different routes. (
Ref. 0012/
0016)
(3S,3'S)- and (3R,3'R)-Astaxanthin --- C15-Phosphonium salts were prepared from enantiomeric 3-acetoxy-4-oxo-
b-ionones obtained by separation of the corresponding diastereomeric camphanates and by microbial resolution. (
Ref. 0015/
0073)
Only Phaffia rhodozyma (Xanthophyllomyces dendrorhous) (yeast) synthesizes (3R,3'R)-astaxanthin, while other organisms, such as bacteria and green algae, synthesize (3S,3'S)-form (
Ref. 0425).
b-Ionone, an end ring analog of
b-carotene, inhibits astaxanthin synthesis from
b-carotene in the Phaffia rhodozyma (
Ref. 1267).
Almost the same stereochemical composition in astaxanthin, its monoester and its diester in krill are found: 62-71% (3R,3'R)-, 11-14% (3R,3'S; meso)- and 17-26% (3S,3'S)-astaxanthin (
Ref. 0422). Those in Euphausia, Thysanoessa, Calanus, Acanthephyra and Cancer (Crustaceans) are also reported (
Ref. 1257).
Semi-empirical molecular orbital calculations using AM1 Hamiltonian (MNDO-AM1 method) were performed in order to predict their stable structures (
Ref. 1337).
[0010]
| AUTHOR | : | Widmer,E., Zell,R., Lukác,T., Casadei,M.,S chönholzer,P., and Broger,E.A. |
| TITLE | : | Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus Oxo-isophoron. I. Modifizierung der Kienzle-Mayer-Synthese von (3S,3'S)-Astaxanthin |
| JOURNAL | : | Helv. Chim. Acta |
| VOL | : | 64 PAGE : 2405 -2418 (1981) |
[0012]
| AUTHOR | : | Zell,R., Widmer,E., Lukác,T., Leuenberger,H.G.W., Schönholzer,P., and Broger,E.A. |
| TITLE | : | Technische Verfahren zur Synthese von Carotinoiden und verwandten Verbindungen aus 6-Oxo-isophoron. III. Ein neues Konzept für die Synthese der enantiomeren Astaxanthine |
| JOURNAL | : | Helv. Chim. Acta |
| VOL | : | 64 PAGE : 2447 -2462 (1981) |
[0015]
| AUTHOR | : | Manchand,P.S. (1996) Carotenoids Volume 2: Synthesis Chapter 2: Coupling Reactions Part II: Organometallic Reactions (Britton,G.,Liaaen-Jensen,S., and Pfander,H., eds), pp55-78, Birkhäuser Verlag,Basel,Boston,Berlin |
| TITLE | : | |
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[0016]
| AUTHOR | : | Ernst,H. (1996) Carotenoids Volume 2: Synthesis Chapter 2: Coupling Reactions Part III: Wittig Olefination (Britton,G.,Liaaen-Jensen,S., and Pfander,H., eds), pp79-102, Birkhäuser Verlag,Basel,Boston,Berlin |
| TITLE | : | |
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| VOL | : | PAGE : - () |
[0058]
| AUTHOR | : | Bjfrnland,T. and Aguilar-Martinez,M. |
| TITLE | : | Carotenoids in red algae |
| JOURNAL | : | Phytochemistry |
| VOL | : | 15 PAGE : 291 -296 (1976) |
[0068]
| AUTHOR | : | Yokoyama, A., Izumida, H., and Miki, W. |
| TITLE | : | Production of Astaxanthin and 4-Ketozeaxanthin by the Marine Bacterium, Agrobacterium aurantiacum |
| JOURNAL | : | Biosci. Biotechnol. Biochem. |
| VOL | : | 58 PAGE : 1842 -1844 (1994) |
[0069]
| AUTHOR | : | Pfander,H., and Riesen,R. (1995) Carotenoids Volume 1A: Isolation and Analysis Chapter 6: Chromatography: Part IV High-Performance Liquid Chromatography (Britton,G.,Liaaen-Jensen,S., and Pfander,H., eds), pp145-190, Birkhäuser Verlag,Basel,Boston,Berlin |
| TITLE | : | |
| JOURNAL | : | |
| VOL | : | PAGE : - () |
[0070]
| AUTHOR | : | Maoka,T.,Komori,T., and Matsuno,T. |
| TITLE | : | Direct diastereomeric resolution of carotenoids I. 3-Hydroxy-4-oxo-b-end group |
| JOURNAL | : | J. Chromatogr. |
| VOL | : | 318 PAGE : 122 -124 (1985) |
[0071]
| AUTHOR | : | Englert,G., and Vecchi,M. |
| TITLE | : | trans/cis Isomerization of Astaxanthin Diacetate/Isolation by HPLC and Identification by 1H-NMR Spectroscopy of Three Mono-cis- and Six Di-cis-Isomers |
| JOURNAL | : | Helv. Chim. Acta |
| VOL | : | 63 PAGE : 1711 -1718 (1980) |
[0073]
| AUTHOR | : | Becher,E.,Albrecht,R.,Bernhard,K.,Leuenberger,H.G.W.,Mayer,H.,Müller,R.K.,Schüep,W., and Wagner,H.P. |
| TITLE | : | Synthese von Astaxanthin aus b-Jonon. I. Erschliessung der enantiomeren C15-Wittig salze durch chemische und mikrobiologishe Racematspaltung von ( )-3-Acetoxy-4-oxo-b-jonon |
| JOURNAL | : | Helv. Chim. Acta |
| VOL | : | 64 PAGE : 2419 -2435 (1981) |
[0077]
| AUTHOR | : | Bernhard,K.,Englert,G.,Mayer,H.,Müller,R.K.,Rüttimann,A.,Vecchi,M.,Widmer,E., and Zell,R. |
| TITLE | : | Synthese von optisch aktiven, natürlichen Carotenoiden und strukturell verwandten Naturprodukten IX. Synthese von (3R)-Hydroxyechinenon, (3R,3'R)- und (3R,3'S)-Adnixanthin, (3R)-Adonirubin, deren optischen Antipoden und verwandten Verbindungen |
| JOURNAL | : | Helv. Chim. Acta |
| VOL | : | 64 PAGE : 2469 -2484 (1981) |
[0088]
| AUTHOR | : | Di Mascio, P., Kaiser, S., and Sies, H. |
| TITLE | : | Lycopene as the most efficient biological carotenoid singlet oxygen quencher PubMed ID:2802626 |
| JOURNAL | : | Arch Biochem Biophys. |
| VOL | : | 274 PAGE : 532-538 (1989) |
[0092]
| AUTHOR | : | Lim, B. P., Nagao, A., Terao, J., Tanaka, K., Suzuki, T., and Takama, K. |
| TITLE | : | Antioxidant activity of xanthophylls on peroxyl radical-mediated phospholipid peroxidation PubMed ID:1627620 |
| JOURNAL | : | Biochim Biophys Acta. |
| VOL | : | 1126 PAGE : 178-184 (1992) |
[0093]
| AUTHOR | : | Terao, J. |
| TITLE | : | Antioxidant activity of beta-carotene-related carotenoids in solution PubMed ID:2779372 |
| JOURNAL | : | Lipids. |
| VOL | : | 24 PAGE : 659-661 (1989) |
[0208]
| AUTHOR | : | Yokoyama, A., and Miki, W. |
| TITLE | : | Composition and Presumed Biosynthetic Pathway of Carotenoids in the Astaxanthin-Producing Bacterium Agrobacterium aurantiacum |
| JOURNAL | : | FEMS Microbiol. Lett. |
| VOL | : | 128 PAGE : 139 -144 (1995) |
[0213]
| AUTHOR | : | Jyonouchi, H., Zhang, L., and Tomita, Y. |
| TITLE | : | Studies of immunomodulating actions of carotenoids. II. Astaxanthin enhances in vitro antibody production to T-dependent antigens without facilitating polyclonal B-cell activation PubMed ID:8346076 |
| JOURNAL | : | Nutr Cancer. |
| VOL | : | 19 PAGE : 269-280 (1993) |
[0215]
| AUTHOR | : | Miki,W. |
| TITLE | : | Biological Functions and Activities of Animal Carotenoids |
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| VOL | : | 63 PAGE : 141 -146 (1991) |
[0218]
| AUTHOR | : | Tanaka, T., Morishita, Y., Suzui, M., Kojima, T., Okumura, A., and Mori, H. |
| TITLE | : | Chemoprevention of mouse urinary bladder carcinogenesis by the naturally occurring carotenoid astaxanthin PubMed ID:8293542 |
| JOURNAL | : | Carcinogenesis. |
| VOL | : | 15 PAGE : 15-19 (1994) |
[0219]
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| TITLE | : | Chemoprevention of rat oral carcinogenesis by naturally occurring xanthophylls, astaxanthin and canthaxanthin PubMed ID:7664280 |
| JOURNAL | : | Cancer Res. |
| VOL | : | 55 PAGE : 4059-4064 (1995) |
[0230]
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| TITLE | : | Carotenooids as Singlet Oxygen Quenchers in Marine Organisms. |
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| VOL | : | 62 PAGE : 134 -137 (1996) |
[0418]
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| TITLE | : | Natural occurrence of enatiomeric and meso-astaxanthin 1. Ex Lobster Eggs (Homarus gammarus) |
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[0419]
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| TITLE | : | Natural Occurrences of enantiomeric and meso-astaxanthin 5, Ex Wild salmon (Salmo salar and Oncorynchus) |
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| VOL | : | 64 PAGE : 449 -457 (1981) |
[0420]
| AUTHOR | : | Bernhard,K.,Englert,G.,Meister,W.Vecchi,M.,Renstrom,B., and Liaaen-Jensen,S. |
| TITLE | : | Carotenoids of the carotenoprotein asteriarubin. Optical purity of asterinic acid |
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| VOL | : | 65 PAGE : 2224 -2229 (1982) |
[0421]
| AUTHOR | : | Matsuno,T.,Maoka,T.,Katsuyama, M.,Ookubo,M.,Katagiri,K., and Jimura,H. |
| TITLE | : | The occurence of enantiomeric and meso-astaxanthin in aquatic animals |
| JOURNAL | : | Bull. Jap. Soc. Sci. Fish. |
| VOL | : | 50 PAGE : 1589 -1592 (1984) |
[0422]
| AUTHOR | : | Maoka,T.,Katsuyama,M.,Kaneko,N., and Matsuno,T. |
| TITLE | : | Stereochemical investigation of the carotenoids in the antarctic krill Euphausia superba |
| JOURNAL | : | Bull. Jap. Soc. Sci. Fish. |
| VOL | : | 51 PAGE : 1671 -1673 (1985) |
[0423]
| AUTHOR | : | Maoka,T.,Tsushima,M., and Matsuno,T. |
| TITLE | : | New acetylenic carotenoids from the starfishes Asterina pectinifera and Asterias amurensis |
| JOURNAL | : | Comp. Biochem. Physiol. |
| VOL | : | 93 PAGE : 829 -834 (1989) |
[0424]
| AUTHOR | : | Maoka,T.,Yokoi,S., and Matsuno,T. |
| TITLE | : | Comparative biochemical studies of carotenoids in nine species of cephalopoda |
| JOURNAL | : | Comp. Biochem. Physiol. |
| VOL | : | 92 PAGE : 247 -250 (1989) |
[0425]
| AUTHOR | : | Andrewes,A.G., and Starr,M.P. |
| TITLE | : | (3R,3'R)-Astaxanthin from the yeast Phaffia rhodozyma |
| JOURNAL | : | Phytochemistry |
| VOL | : | 15 PAGE : 1009 -1011 (1976) |
[0441]
| AUTHOR | : | Hirayama, O., Nakamura, K., Hamada, S., and Kobayasi, Y. |
| TITLE | : | Singlet oxygen quenching ability of naturally occurring carotenoids PubMed ID:8152349 |
| JOURNAL | : | Lipids. |
| VOL | : | 29 PAGE : 149-150 (1994) |
[1164]
| AUTHOR | : | Turujman, S.A. |
| TITLE | : | Rapid direct resolution of the stereoisomers of all-trans astaxanthin on a Pirkle covalent L-leucine column |
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| VOL | : | 631 PAGE : 197 -199 (1993) |
[1257]
| AUTHOR | : | Foss, P., Renstrøn, B., Liaaen-Jensen, S. |
| TITLE | : | Natural occurrence of enantiomeric and meso astasanthin: 7. Crustaceans including zooplankton |
| JOURNAL | : | Comp. Biochem. Physiol. B |
| VOL | : | 86 PAGE : 313 -314 (1987) |
[1267]
| AUTHOR | : | Lewis, M.J., Ragot, N., Berlant, M.C., Miranda, M. |
| TITLE | : | Selection of astaxanthin-overproducing mutants of Phaffia rhodozyma with b-ionone PubMed ID:16348304 |
| JOURNAL | : | Appl. Environ. Microbiol. |
| VOL | : | 56 PAGE : 2944 -2945 (1990) |
[1337]
| AUTHOR | : | Hashimoto, H., Yoda, T., Kobayashi, T., Young, A.J. |
| TITLE | : | Molecular structures of carotenoids as predicted by MNDO-AM1 molecular orbital calculations |
| JOURNAL | : | J. Mol. Struct. |
| VOL | : | 604 PAGE : 125 -146 (2002) |
Last updated June 19, 2007. Copyright © 1989-2007 Japanese Conference on the Biochemistry of Lipids (JCBL). All rights reserved.
